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United States Patent |
5,147,417
|
Nemser
|
*
September 15, 1992
|
Air-intake system for mobile engines
Abstract
An air intake system for a mobile combustion engine is disclosed. The air
intake system comprises a membrane formed from an amorphous polymer of
perfluoro-2,2-dimethyl-1,3-dioxole, the membrane exhibiting an
oxygen-nitrogen selectivity of at least 1.4:1. Either the permeate section
or the feed section of the membrane is adapted to be in fluid flow
communication with a combustion zone of the mobile combustion engine. The
membrane preferably has an oxygen flus in excess of 100 Barrers,
especially in excess of 500 Barrers. The air intake system provides either
oxygen-enriched air or oxygen-deplected air for the engine, depending on
the mode of operation of the engine.
Inventors:
|
Nemser; Stuart M. (Wilmington, DE)
|
Assignee:
|
Du Pont Canada Inc. (Mississauga, CA)
|
[*] Notice: |
The portion of the term of this patent subsequent to September 24, 2008
has been disclaimed. |
Appl. No.:
|
724700 |
Filed:
|
July 2, 1991 |
Current U.S. Class: |
95/54; 96/8; 96/12; 123/26 |
Intern'l Class: |
B01D 053/22; B01D 071/32 |
Field of Search: |
55/16,68,158
123/25 A,26
|
References Cited
U.S. Patent Documents
3308107 | Mar., 1967 | Selman et al. | 55/16.
|
4174955 | Nov., 1979 | Blackmer et al. | 55/16.
|
4530569 | Jul., 1985 | Squire | 526/247.
|
4553988 | Nov., 1985 | Shimizu et al. | 55/158.
|
4565855 | Jan., 1986 | Anderson et al. | 526/247.
|
4754009 | Jun., 1988 | Squire | 526/247.
|
4883023 | Nov., 1989 | Tsang et al. | 55/158.
|
4950315 | Aug., 1990 | Gollan | 55/158.
|
5051113 | Sep., 1991 | Nemser | 55/16.
|
Foreign Patent Documents |
0024718 | Mar., 1981 | EP | 55/16.
|
0108426 | May., 1984 | EP | 55/158.
|
56-166903 | Dec., 1981 | JP | 55/158.
|
59-212632 | Dec., 1984 | JP | 55/158.
|
60-102901 | Jun., 1985 | JP | 55/158.
|
61-078419 | Apr., 1986 | JP | 55/158.
|
61-146320 | Jul., 1986 | JP | 55/158.
|
61-149225 | Jul., 1986 | JP | 55/158.
|
61-157325 | Jul., 1986 | JP | 55/158.
|
62-169923 | Jul., 1987 | JP | 55/16.
|
62-183837 | Aug., 1987 | JP | 55/158.
|
63-156514 | Jun., 1988 | JP | 55/158.
|
1-063021 | Mar., 1989 | JP | 55/158.
|
0345717 | Jun., 1979 | SU | 55/16.
|
2122103A | Jan., 1984 | GB.
| |
Primary Examiner: Spitzer; Robert
Parent Case Text
RELATED PATENT APPLICATION
This patent application is a continuation-in-part of my patent application
Ser. No. 07/538,058, filed Jun. 13, 1990, now U.S. Pat. No. 5,051,113.
Claims
I claim:
1. A process for the operation of a mobile combustion engine having a
combustion zone an air intake system for the combustion zone comprising
feeding air to a feed side of an oxygen enrichment membrane in the air
intake system in a manner that causes an oxygen enriched portion of the
air to permeate the membrane to a permeate side of the membrane, and then
feeding air from one of the permeate side and the feed side to the
combustion zone of the mobile combustion engine, for oxygen enrichment
membrane comprising a film or coating of an amorphous polymer of
perfluoro-2-2- dimethyl-1,3--dioxole on a porous support, said membrane
exhibiting an oxygen/nitrogen selectivity of at least 1.4:1.
2. The process of claim 1 in which air from the permeate side of the
membrane is fed to the combustion zone.
3. The process of claim 1 in which air from the feed side of the membrane
is fed to the combustion zone.
4. The process of claim 3 in which the membrane has an oxygen flux in
excess of 100 Barrers.
5. The process of claim 3 in which the membrane is in the form of a
plurality of hollow fibres.
6. The process of claim 5 in which the air intake system is connected to
the interior of the fibres.
7. The process of claim 5 in which the air intake system is connected to
the exterior of the fibres.
8. The process of claim 3 in which the membrane is in the form of a
composite membrane.
9. The process of claim 3 in which the permeate section is under vacuum.
10. An air intake system for a mobile combustion engine, said air intake
system comprising a membrane comprising a film or coating of an amorphous
polymer of perfluoro-2,2-dimethyl-1,3-dioxole on a porous support, said
membrane exhibiting an oxygen/nitrogen selectivity of at least 1.4:1, said
air intake system being adapted to provide either oxygen-enriched air or
oxygen-depleted air to a combustion zone of the mobile combustion engine.
11. The air intake system of claim 10 which is adapted to provide
oxygen-enriched air to a combustion zone of the mobile combustion engine.
12. The air intake system of claim 10 which is adapted to provide
oxygen-depleted air to a combustion zone of the mobile combustion engine.
13. The air intake system of claim 12 in which the membrane has an oxygen
flux in excess of 100 Barrers.
14. The air intake system of claim 13 in which the membrane has an oxygen
flux in excess of 500 Barrers.
15. The air intake system of claim 12 in which the selectivity of oxygen
over nitrogen is at least 1.7:1.
16. The air intake system of claim 12 in which the membrane is in the form
of a plurality of hollow fibres.
17. The air intake system of claim 16 in which the air intake system is
connected to the interior of the fibres.
18. The air intake system of claim 16 in which the air intake system is
connected to the exterior of the fibres.
19. The air intake system of claim 12 in which the membrane is in the form
of a composite membrane.
20. A mobile combustion engine comprising a combustion zone and an air
intake system for the combustion zone, the air intake system comprising an
oxygen enrichment membrane comprising a film or coating of an amorphour
polymer of perfluoro-2,2-dimethyl-1,3-dioxole on a porous support, said
membrane exhibiting an oxygen/nitrogen selectively of at lest 1.4:1, said
membrane having an air feed section and a permeate section with one of the
permeate section and the feed section being in fluid flow communication
with the combustion zone.
21. The mobile combustion engine of claim 20 in which the permeate section
of the membrane is in fluid flow communication with the combustion zone.
22. The mobile combustion engine of claim 20 in which the feed section of
the membrane is in fluid flow communication with the combustion zone.
23. The mobile combustion engine of claim 22 in which the membrane has an
oxygen flux in excess of 100 Barrers.
24. The mobile combustion engine of claim 23 in which the membrane has an
oxygen flux in excess of 500 Barrers.
25. The mobile combustion engine of claim 22 in which the selectivity of
oxygen over nitrogen is at least 1.7:1.
26. The mobile combustion engine of claim 22 in which the membrane is in
the form of a plurality of hollow fibres.
27. The mobile combustion engine of claim 26 in which the air intake system
is connected to the interior of the fibres.
28. The mobile combustion engine of claim 26 in which the air intake system
is connected to the exterior of the fibres.
29. The mobile combustion engine of claim 22 in which the membrane is in
the form of a composite membrane.
Description
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to an air intake system for mobile engines,
especially an air intake system for automotive engines, and in particular
to an air intake system that has a selectively permeable membrane to
effect oxygen enrichment or oxygen depletion of the air entering into the
intake.
2. Description of the Prior Art
Methods for the enrichment of and/or separation of gaseous admixtures,
including gaseous admixtures of oxygen and nitrogen e.g. air, are known.
In particular, a membrane formed from a polymer of a perfluorodioxole is
described in PCT patent application No. W090/15662 of S.M. Nemser and I.D.
Roman, published Dec. 27, 1990. These applications describe a selectively
permeable membrane, for the separation of a wide variety of gaseous
admixtures, formed from an amorphous polymer of
perfluoro-2,2-dimethyl-1,3- dioxole. The membrane may be a supported
membrane, in the form of a film or a coating on a porous support or in the
form of a hollow fibre. The membrane may be used for the separation of
gaseous admixtures of organic compounds e.g. gaseous fluorocarbons or
volatile organic compounds, from other gases. In addition, the membranes
may be used for the separation of a wide variety of gaseous mixtures,
including oxygen from nitrogen i.e. to enrich air in the amount of oxygen
contained therein.
The use of membrane oxygen enrichment in natural gas combustion is
described by S. G. Kimura and W. R. Browall in Journal of Membrane
Science, 29(1986)69-77. The article states that combustion with oxygen
enriched air can substantially reduce fuel consumption in certain
applications and the use of a membrane is a potentially attractive
approach for producing oxygen enriched air. A silicone based oxygen
enrichment membrane was fabricated and tested, giving a reduction in
natural gas consumption.
Apparatus for increasing or decreasing the oxygen fraction of air to be
conveyed to a consumer is disclosed by F. Wolff in published European
patent application 0 024 718, published Mar. 11, 1990. Apparatus for
purifying the air contained in a confined space e.g. the passenger cabin
of an automobile, is disclosed in published UK patent application 2 122
103 of M. Yamamoto et al, published Jan. 11, 1984.
SUMMARY OF THE INVENTION
An automotive air intake system for a mobile combustion engine has now been
found, the system being formed from a membrane comprised of an amorphous
polymer of perfluoro-2,2-dimethyl-1,3-dioxole.
Accordingly, the present invention provides an air intake system for a
mobile combustion engine, said air intake system comprising a membrane
formed from an amorphous polymer of perfluoro-2,2-dimethyl-1,3-dioxole,
said membrane exhibiting an oxygen/nitrogen selectivity of at least 1.4:1.
In a preferred embodiment of the air intake system, the membrane has an air
feed section and a permeate section, said permeate section being adapted
to be in fluid flow communication with a combustion zone of the mobile
combustion engine.
The present invention also provides a mobile combustion engine having a
combustion zone, and an air intake system for the combustion zone, in
which the air intake system comprises an oxygen enrichment membrane formed
from an amorphous polymer of perfluoro-2,2-dimethyl-1,3-dioxole, said
membrane exhibiting an oxygen/nitrogen selectivity of at least 1.4:1, said
membrane having an air feed section and a permeate section with the
permeate section being in fluid flow communication with the combustion
zone.
The present invention further provides a process for the operation of a
mobile combustion engine having a combustion zone, and an air intake
system for the combustion zone, in which the air intake system comprises
an oxygen enrichment membrane formed from an amorphous polymer of
perfluoro-2-2-dimethyl-1,3-dioxole, said membrane exhibiting an
oxygen/nitrogen selectivity of at least 1.4:1, said membrane having an air
feed section and a permeate section, comprising feeding air to the feed
section of the membrane and feeding oxygen enriched air from the permeate
section to the combustion zone of the mobile combustion engine, said
permeate section preferably operating under vacuum.
In embodiments of the present invention, the membrane has a flux in excess
of 100 Barrers.
In a further embodiment of the present invention, the membrane is in the
form of a plurality of hollow fibres, especially hollow fibres in which
the air intake system is connected to the interior of the fibres.
DETAILED DESCRIPTION OF THE INVENTION
The present invention is illustrated by the embodiments shown in the
drawings in which:
FIG. 1 is a schematic representation of an air intake system of the
invention; and
FIG. 2 is a schematic representation of a cross-section of the air intake
system of FIG. 1, through 2--2.
An embodiment of the air intake system of the invention is shown in FIG. 1,
being generally referred to by 1. Air intake system 1 is comprised of a
cylinder 2 having end caps 3 and 4. End cap 3 is on the inlet end of
cylinder 2, and end cap 4 is on the outlet end of cylinder 2. Cylinder 2
is filled with a plurality of hollow fibres (not shown).
End cap 3 is also fitted with air inlet pipe 7 that has a filter 8 in-line
with air inlet pipe 7; filter 8 may be conveniently in the form of a
filter and a valve for control of flow of air entering into air inlet pipe
7. Air inlet pipe 7 may be fitted with pump means in order to facilitate
flow of air into the inlet pipe.
End cap 4 has a first outlet pipe 10 having an exhaust outlet 11. End cap 4
is also fitted with second outlet pipe 12 that is fitted with a connector
13. Connector 13 is intended to be attached to means for fluid flow
communication with the combustion zone of the mobile combustion engine
(not shown).
Inlet pipe 7 may be connected to and in fluid flow communication with the
interior of the hollow fibres located inside cylinder 2. In that event,
first outlet pipe 10 is also connected to and in fluid flow communication
with the interior of the hollow fibres, and second outlet pipe 12 is
connected to and in fluid flow communication with the exterior of the
fibres. Alternatively, inlet pipe 7 is connected to and in fluid flow
communication with the exterior of the hollow fibres located inside
cylinder 2, and the outlet pipes would be connected in the opposite manner
to that described above. Thus, the air intake system 1 shown in FIG. 1 may
have inlet pipe 7 in fluid flow communication either with the interior or
passed the exterior of the hollow fibres, with the outlet pipes connected
accordingly.
FIG. 2 shows a cross-section of cylinder 2, with a plurality of hollow
fibres 20, also shown in cross-section. Inlet pipe 7 is also shown.
In FIGS. 1 and 2, the membrane has been referred to as being a hollow
fibre. Although this is believed to be the preferred configuration of the
membrane, other shapes may be used e.g. the membranes may be generally
referred to as membranes in the form of films or coatings, including in
the form of spiral cartridges; moreover, the membranes may be of
constructions known to those skilled in the art including so-called
monolithic membranes, asymmetric membranes and composite membranes. The
membranes must be thin, in order to maximize the rate of gas transmission
through the membrane, preferably less than 0.01 mm and especially less
than 0.001 mm in thickness; in the case of composite membranes, such
thickness refers to the thickness of the layer or coating of the amorphous
polymer.
In operation, air is fed in through air inlet pipe 7, passes either through
or over the exterior of the hollow fibres 20 i.e to the feed side of the
membrane, depending on the method of connection of inlet pipe 7, and exits
through first outlet 10. Oxygen preferentially passes through the membrane
i.e. the hollow fibres, such that the air on the permeate side is enriched
in oxygen. The permeate side of the hollow fibre membrane will usually be
operated under a partial vacuum e.g. it will be connected to the
combustion zone of the mobile combustion engine. The permeate zone may be
the sole source of oxygen for the combustion zone, but it may be
preferable to have a supplementary source of oxygen e.g. air, that is also
in fluid flow communication with the combustion zone. Appropriate valving
means may be used to control the addition of supplementary amounts of air,
especially based on the instantaneous demand of the combustion engine for
oxygen.
FIG. 1 shows the inlet air and outlet enriched air being in a co-current
relationship. It is to be understood, however, that the inlet air and
outlet enriched air may also be in a counter-current relationship with the
outlet for the enriched air i.e. second outlet pipe 12, being on the same
end of cylinder 2 as inlet pipe 7. Second outlet pipe 12 may also be
located between end cap 3 and end cap 4.
While the invention has been discussed above with particular reference to
enrichment of air with oxygen and the feeding of oxygen-enriched air to a
mobile combustion engine, it is to be understood that the present
invention may be used to deplete the amount of oxygen in the air and to
feed oxygen-depleted air to a mobile combustion engine. In the operation
of the invention discussed above, air from the permeate side of the
membrane, which is enriched in oxygen, is fed to the combustion engine. If
oxygen-depleted air is to be used, air from the permeate side of the
membrane would be fed to the combustion engine. Both oxygen-enriched air
and oxygen-depleted air could be used in the operation of combustion
engines, in different engines or in different aspects of the operation of
an engine.
Use of oxygen-enriched air would be expected to reduce the level of
hydrocarbon emissions but increase the level of NO.sub.x emissions in both
gasoline and diesel engines. Conversely, use of oxygen-depleted air would
be expected to increase the level of hydrocarbon emissions but reduce the
level of NO.sub.x emissions in both gasoline and diesel engines. In
addition, oxygen-enriched air would be expected to increase the brake
specific horsepower and improve or increase the rate of operation of
catalytic converters in gasoline engines. It should be understood,
however, that an increase in emissions through the use of oxygen enriched
or depleted air is not necessarily detrimental to the environment because
for instance it is the total emission that must be considered, not just
any particular substance, and other steps may be taken to reduce
emissions.
The selectively permeable membrane is formed from an amorphous polymer of
perfluoro-2,2-dimethyl- 1,3-dioxole. In embodiments, the polymer is a
homopolymer of perfluoro-2,2-dimethyl-1,3-dioxole. In other embodiments,
the polymer is a copolymer of perfluoro-2,2-dimethyl-1,3-dioxole,
including copolymers having a complementary amount of at least one monomer
selected from the group consisting of tetrafluoroethylene, perfluoromethyl
vinyl ether, vinylidene fluoride and chlorotrifluoroethylene. In one
preferred embodiment, the polymer is a dipolymer of
perfluoro-2,2-dimethyl-1,3-dioxole and a complementary amount of
tetrafluoroethylene, especially such a polymer containing 65-99 mole % of
perfluoro-2,2-dimethyl-1,3-dioxole. The amorphous polymer preferably has a
glass transition temperature of at least 140.degree. C., and more
preferably at least 180.degree. C. Glass transition temperature (T.sub.g)
is known in the art and is the temperature at which the polymer changes
from a brittle, vitreous or glassy state to a rubbery or plastic state.
Examples of dipolymers are described in further detail in the U.S. Pat.
No. 4,754,009 of E. N. Squire.
The glass transition temperature of the amorphous polymer will vary with
the actual polymer of the membrane, especially the amount of
tetrafluoroethylene or other comonomer that may be present. Examples of
T.sub.g are shown in FIG. 1 of the aforementioned U.S. Pat. No. 4,754,009
of E. N. Squire as ranging from about 260.degree. C. for dipolymers with
tetrafluoroethylene having low amounts of tetrafluoroethylene comonomer
down to less than 100.degree. C. for the dipolymers containing at least 60
mole % of tetrafluoroethylene.
The membranes of the present invention may be manufactured by a variety of
methods known to those skilled in the art, particularly in the light of
the versatile processability of the perfluorodioxole polymers. These
methods include solvent and melt film-casting and fibre-casting methods,
as well as coating techniques.
The gaseous admixture fed to the air intake system will normally be in the
form of air, especially ambient air. The membranes used in the air intake
system of the present invention are capable of being used at elevated
temperature, including in some embodiments at temperatures above
100.degree. C. The air intake systems may be operated at such elevated
temperature especially temperatures of up to 90.degree. C. and in
particular up to 50.degree. C. Such temperatures may be achieved, for
example, by heat exchange of inlet air with exhaust gases from the
combustion engine. However, the membranes should be used at a temperature
below the glass transition temperature, and especially at least 30.degree.
C. below the glass transition temperature, of the amorphous polymer used
to form the membrane; these capabilities are beyond the normal operating
requirements for automotive end-uses. In preferred embodiments, the glass
transition temperature is at least 140.degree. C. and especially at least
180.degree. C. The method of the present invention may be operated at
relatively low temperatures e.g. below 0.degree. C.
The gas admixture may originate from a wide variety of sources. For
example, the gaseous admixture may be air, or an admixture derived from
air e.g. an admixture that has been enriched or depleted in oxygen using
for example the method of the present invention.
As exemplified hereinafter, oxygen and nitrogen tend to preferentially pass
through the selectively permeable membranes, with oxygen being passed in
preference to nitrogen, and does so at high flux. In preferred embodiments
of the present invention, the membrane has a permeability to oxygen of at
least 100 Barrers, especially at least 200 Barrers and preferably at least
500 Barrers. Preferably, the membrane has a selectivity of oxygen over
nitrogen of at least 1.7:1.
The perfluorodioxoles membranes described herein with respect to the
present invention are expected to be outstanding membrane materials for
air intake systems for mobile combustion engines, including both gasoline
and diesel engines, and for the supply of oxygen-enriched air or
oxygen-depleted air. In preferred embodiments of the air intake systems
using the membranes described herein, the air intake system (excluding
pipes or other means of fluid flow communication to the combustion zone)
preferably occupies less than 56 000 cm.sup.3, especially less than 28 000
cm.sup.3 and more preferably less than 14 000 cm.sup.3. In addition, the
surface area of the membrane is preferably less than 460 m.sup.2 and more
preferably less than 230 m.sup.2 ; in embodiments the surface area is less
than 140 m.sup.2 and especially less than 90 m.sup.2.
In embodiments, the air intake system of the present invention will provide
oxygen-enriched air containing 23-35% of oxygen, especially 23-27% of
oxygen, for enhanced combustion. The examples hereinafter show that
membranes described herein exhibit exceptionally high gas permeabilities,
at relatively low selectivity; such peraeability characteristics are
suitable for the end-use described herein. In alternate embodiments, the
air intake system will provide oxygen-depleted air containing less than
21% oxygen, for example containing 6-19% of oxygen and especially 15-19%
of oxygen.
In Examples I-IV hereinafter, gas permeation properties of the
perfluorodioxole polymers were measured using samples of dense film
membranes. The samples were cut into discs and mounted in a permeation
cell, so as to form a feed gas chamber and a permeate gas chamber, the
latter being operated at lower pressure.
In the air separation tests, the feed stream was compressed air, which was
provided at a flow rate that was high enough to ensure a constant
feed-stream composition; the permeate oxygen-enriched air was removed at
atmospheric pressure. Permeate flow rate was measured by the volumetric
displacement of a soap bubble in a calibrated burette, and permeate
composition was determined by gas chromatography. In most of the
single-gas permeation tests, the feed gas was provided at a pressure
ranging from 21 kPa to 3500 kPa.
In some low pressure tests, the permeate gas flow rate was determined by
measuring the rate of increase in pressure in a constant volume evacuated
chamber. The permeability of the polymers for the gas was determined from
the volume of the evacuated chamber and the thickness and surface area of
the membrane.
The present invention is illustrated by the following examples.
EXAMPLE I
Membranes having a thickness of 0.25 mm were melt pressed from a dipolymer
of perfluoro-2,2dimethyl-1,3-dioxole and tetrafluoroethylene having a
glass transition temperature of 253.degree. C.
In single-gas and mixed gas premeation tests, using the premeation test
method described above, the films exhibited exceptionally high
permeability toward the components of air viz. 990 Barrers with respect to
oxygen and 490 Barrers with respect to nitrogen; a Barrer is defined by
the following formula: Barrer =10.sup.-10 {Cm.sup.3
(STP).cm}/{cm.sup.2.sec.cmHg}Furthermore, it was found that the oxygen and
nitrogen permeabilities were not functions of the feed pressures, nor of
the membrane thickness.
EXAMPLE II
Membranes were prepared from a dipolymer of
perfluoro-2,2-dimethyl-1,3-dioxole and tetrafluoroethylene having a glass
transition temperature of 166.degree. C. using melt pressing and solvent
casting techniques. The melt pressed films had a thickness of 0.25 mm and
the solvent cast films had a thickness of 0.025 mm.
The solvent cast films were formed from solution (15% by weight of the
dipolymer in FC-75; FC-75 is the tradename of a commercial solvent
available from 3M Company, and is perfluoro (2-butyl tetrahydrofuran)).
Membranes having a thickness of 0.38 mm were cast from the solution onto a
glass plate and the solvent was allowed to evaporate slowly; the dry
membrane of the dipolymer that was obtained had a thickness of 0.025 mm.
The films were subjected to single-gas permeation tests using the procedure
described above, using air and nitrogen. The results obtained was
summarized in Table II.
Permeation results are summarized in Table II.
TABLE II
______________________________________
Gas Membrane Thickness
Feed Pressure
Permeability
______________________________________
O.sub.2
0.250 mm 3.55 MPa air 350 Barrer
O.sub.2
0.025 mm 0.79 MPa air 340 Barrer
N.sub.2
0.250 mm 3.55 MPa air 130 Barrer
N.sub.2
0.025 mm 0.79 MPa air 130 Barrer
______________________________________
The results show that, for oxygen and nitrogen, membrane thickness had no
apparent effect on the permeability results obtained.
The results also indicate that the dipolymer of this Example exhibits lower
permeability than the dipolymer of Example I; the latter had a higher
content of perfluoro-2,2-dimethyl-1,3-dioxole. However, permeability
towards the components of air is still exceptionally high, being at least
two orders of magnitude higher than polytetrafluoroethylene.
EXAMPLE III
Membranes with a thickness of 0.25 mm were melt-pressed from three
dipolymers of perfluoro-2,2-dimethyl-1,3-dioxole and tetrafluoroethylene
of different dioxole contents and glass transition temperatures (Tg). The
average results of air separation tests using air with a feed stream
pressure of 700-3500 kPa are given in Table III.
TABLE III
______________________________________
Dioxole Permeability to
Selectivity
(mole %) Tg O.sub.2 O.sub.2 /N.sub.2
______________________________________
66 166.degree. C.
340 Barrer 2.6
76 203.degree. C.
380 Barrer 2.3
86 253.degree. C.
990 Barrer 2.05
______________________________________
In the air-separation tests, these dipolymer membranes exhibited
exceptionally high O.sub.2 and N.sub.2 permeabilities. The membrane
prepared from the lowest Tg-grade dipolymer had the highest O.sub.2
/N.sub.2 selectivity, whereas the membrane prepared from the highest
Tg-grade dipolymer had the highest O.sub.2 permeability and lowest O.sub.2
/N.sub.2 selectivity. In comparison, commercial air separation membranes
formed from glassy polymers tend to be more selective but with
substantially lower flux towards oxygen, with O.sub.2 permeability
typically ranging from about 1.3 Barrer (polysulfone) to 30 Barrer (poly
4-methylpentene); a very small proportion of known membranes or films
exhibit permeabilities in excess of 100 Barrers for oxygen. The results of
Table III also show that membranes of the invention may be prepared with a
range of permeation properties.
EXAMPLE IV
Single-gas permeation tests were conducted using a membrane prepared from a
membrane of the high-Tg dipolymer described in Example III. A number of
different gases were tested. As a comparison, tests were also conducted on
a membrane formed from polytetrafluoroethylene (PTFE).
A number of permeability measurements were conducted, using pressures that
were generally in the range of 350-1750 kPa, it being the understanding
that the permeability of the gases listed in Table IV is only a slight
function of pressure in this pressure range.
The results obtained were given in Table IV.
TABLE IV
______________________________________
Permeability
Gas Dipolymer PTFE
______________________________________
O.sub.2 990 Barrer
4.2 Barrer
N.sub.2 490 Barrer
1.4 Barrer
______________________________________
The results obtained illustrate the high permeability obtainable with the
membranes of the present invention. Whereas the selectivity demonstrated
by the dipolymer and polytetrafluoroethylene membranes are similar, and
believed to be relatively typical of glassy, non-rubbery polymers, the
dipolymer membranes exhibit relatively very high permeability.
EXAMPLE V
Permeation measurements were conducted using a permeation cell that was
immersed in water in a temperature-controlled water bath. The permeate
from the permeation cell was passed through a sampler bulb of a gas
chromatograph, to measure the composition of the permeate, and then to a
soap film capillary to measure the permeate flow rate. Concentrations in
gas mixtures were measured with a HP Gas Chromatograph model 5700A
followed by a Spectra Physics Integrator type model SP4400. Pressure and
pressure drop could be measured in the cell.
The membrane was placed on a porosive sinter (pore size 15-20 microns) and
held in place using two Teflon rings. The effective membrane area for mass
transfer was 9.62 cm.sup.2 (3.5 cm diameter).
When mixtures of gases were being tested, a purging stream with about 10
times the permeate flow rate was used to ensure a constant feed
concentration, and the purged stream was monitored to determine the feed
concentration. For measurements with single gases, the cell was purged at
the beginning of each experiment for a short period of time.
Melt pressed membranes were prepared by placing polymer in a mould and
heating to a temperature of about 20.degree. C. above the glass transition
temperature (Tg). When that temperature was reached, the polymer was
treated by applying pressure and releasing it, using pressures of up to 50
tonnes/12.5 cm diameter of the membrane, for 5 minutes. The mould was then
slowly cooled under a pressure of 40 tonnes/12.5 cm diameter, to room
temperature. The resultant thick powder was transferred to the center of a
flat plate covered by aluminum foil. Another aluminum foil-covered flat
plate was mounted on it, without any spacer. The two plates were heated in
a melt press, at minimal pressure, to a temperature of 100.degree. C.
above Tg, after which the pressure was raised to 40 tonne/12.5 cm
diameter, and the sample was pressed for 10 minutes. The sample was then
cooled slowly to room temperature under pressure, and the aluminum foil
was peeled off carefully.
Cast membranes were prepared from solutions of the polymers in FC-75
solvent. The solution was warmed to 50-60.degree. C., and filtered through
a 3 micron filter. The filtered solution was cast onto clean glass, and
dried at ambient temperature in a dust free environment. The membrane was
further dried in an oven at 80.degree. C. for at least 2 hours, and then
in an oven at 110.degree. C. overnight.
Membranes were formed from a dipolymer of
perfluoro-2,2-dimethyl-1,3-dioxole and tetrafluoroethylene having a glass
transition temperature of 240.degree. C., by solvent casting from a 2.5%
solution in FC-75 solvent using the procedure described above, with the
heating at 110.degree. C. being for 12 hours. The resultant membrane was
20 micron thick.
The mixed gas fed to the permeation cell had the following composition:
N.sub.2 78.25%, O.sub.2 20.67% with the remainder being a fluorocarbon
gas.
Further experimental details and the results obtained are given in Table V.
Measurements were made at 20.degree. C. under steady-state conditions in
this and the following examples, unless stated to the contrary.
TABLE V
______________________________________
Permeability
Pressure (Barrers) Selectivity
(kPa) O.sub.2 N.sub.2 O.sub.2 /N.sub.2
______________________________________
700 242 114 2.1
445 263 112 2.4
______________________________________
The results show that the selectivity and high flux in the presence of
another gas.
EXAMPLE VI
Membranes formed from
poly-[perfluoro(2-methylene-4-methyl-1,3-dioxolane)]i.e. polymer of the
aforementioned U.S. Pat. No. 3,308,107, had been tested for permeability
using a volumetric method at 25.degree. C.
Further experimental details and the results obtained are given in Table
VI.
TABLE VI
______________________________________
Gas Permeability
______________________________________
O.sub.2 *
36 Barrers
N.sub.2 *
10 Barrers
______________________________________
*Results are averages of data for single gases and binary mixtures.
The results show that the polymer of U.S. Pat. No. 3,308,107 exhibit
permeabilities to gases that were substantially lower than those measured
as described above in examples herein, especially in comparison with data
for membranes formed from the homopolymer.
EXAMPLE VII
A membrane of the homopolymer of perfluoro-2,2-dimethyl-1,3-dioxole was
prepared using the solvent casting technique described in Example V; the
membrane thickness was 33 microns. It was tested for permeability using
synthetic air and single gases with a feed pressure of 790 kPa.
The results obtained are given in Table VII.
TABLE VII
______________________________________
Permeability
Gas (24.degree. C.)
______________________________________
He 3600 Barrer
H.sub.2 3300 Barrer
O.sub.2 (air feed)
1540 Barrer
N.sub.2 (air feed)
810 Barrer
N.sub.2 830 Barrer
______________________________________
It is believed that the permeabilities of hydrogen and helium are the
highest measured with these gases, with the exception of
polytrimethylsilylpropyne. The latter polymer, however, is known to have
unstable gas transport properties e.g. see U.S Pat. No. 4,859,215.
Moreover, the permeability of nitrogen in mixed gas tests was similar to
the permeability of nitrogen in single gas tests, which indicates that
there was no measurable interaction between copermeating oxygen and
nitrogen molecules or competition for permeation paths in the polymer.
EXAMPLE VIII
The membrane of Example VII was tested in air separation over a broad range
of feed pressures, to measure the effect of pressure on the permeability
of permanent gases through the homopolymer of
perfluoro-2,2-dimethyl-1,3-dioxole.
The results are given in Table VIII.
TABLE VIII
______________________________________
Pressure of O.sub.2 Flux
O.sub.2 /N.sub.2
Feed Air (Barrer) Selectivity
______________________________________
270 1500 1.95
450 1560 2.0
620 1610 2.0
790 1620 2.0
960 1610 1.95
1140 1610 1.95
1480 1610 1.95
1830 1560 1.9
2170 1550 1.9
______________________________________
The results confirm that the partial pressure across the membrane has
little affect on the permeability of oxygen and nitrogen through the
membrane.
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